Dyeing human hair with aqueous solution of indamines

ABSTRACT

INDAMINES HAVING THE FORMULA   6-HO,7-((4-(HN=),3-R1,2-R2,5-R4,6-R3-CYCLOHEXA-2,5-DIEN-1-   YLIDENE)=N-)-3,4-DIHYDRO-2H-1,4-BENZOXAZINE   WHEREIN R1, R2 R3 AND R4 CAN BE HYDROGEN, HALOGEN LOWER, ALKYL OR LOWER ALKOXY AND ARE USEFULLY EMPLOYED IN A DYE COMPOSITION FOR COLORING KERATINOUS FIBVERS. SUCH COMPOSITIONS ARE AQUEOUS SOLUTIONS OF THE INDAMINES AND CAN BE FORMULATED WITH LOWER, ALKANOLS AND FILM-FORMING COSMETIC RESINS TO PRODUCE HAIR SETTING LOTIONS.

United States Patent 1' Office 3,677,690 'DYEING HUMAN HAIR WITH AQUEOUSSOLUTION OF INDAMINES Gregoire Kalopissis, Paris, Andre Bugaut,Boulogne-sur- Seine, and Francoise Estradier, Paris, France, assignorsto Societe Anonyme dite: LOreal, Paris, France No Drawing. Filed July 6,1970, Ser. No. 52,739

Claims priority, application Iiuxembourg, July 17, 1969,

wherein R R R and R, can be hydrogen, halogen, lower alkyl or loweralkoxy and are usefully employed in a dye composition for coloringkeratinous fibers. Such compositions are aqueous solutions of theindamines and can be formulated with lower alkanols and film-formingcosmetic resins to produce hair setting lotions.

The present invention relates to a novel indamine and a process forpreparing the same and to a novel cosmetic composition containing saidindamine for dyeing keratinic fiber such as human hair. Morespecifically, the present invention relates to a method for preparingand a use of a novel indamine having the formula:

N Flu TOE R. R. 1 7 N: "NH

wherein R R R and R each represent hydrogen, halogen, lower alkyl having1-4 carbon atoms and lower alkoxy containing from 1 to 4 carbon atoms. 1

The novel indamines of this invention can be prepared by condensing aparaphenylenediamine having the formula:

wherein R R R and R have the meanings indicated above, on hydroxy-6phenomorpholine having the formula:

3,677,690 Patented July 18, 1972 This condensation reaction can beperformed in an aqueous or aqueous acetonic medium having a pH equal toor greater than 8 and as high as 12 in the presence of an oxidizingagent, and at a temperature between 0 and 50 C.

The oxidizing agent used in this reaction can be hydrogen peroxide orpotassium persulfate. When the oxidizing agent is hydrogen peroxide, itis present generally in amounts of about 5-20 times the stoichiometricrequirement, and when the oxidizing agent employed is potassiumpersulfate, it is present in amounts of about 1-2 times thestoichiometric requirements. The reaction medium can be made alkaline,preferably by the addition thereto of ammonia, although otheralkalinizing agents such as NaOH and KOH can also be employed.

The paraphenylenediamine used .in the preparation of the indaminesaccording to the present invention can be, for example,paraphenylenediamine, paratoluylenediamine, diamine-2,5 anisole,diamino-2,5 c'hlorobenzene, methoxy- 2 methyl-5 paraphenylenediamine,dimethyl-2,6 methoxyparaphenylenediamine and diamino-1,4 durene. Themole ratio of paraphenylene diamine to hydroxy-6-phenomorpholine in thecondensation reaction can vary between about 3:1 to 0.5 :1 andpreferably between 1:1 to 2:1.

The novel indamines of the present invention constitute dyes that have aparticularly interesting application in dyeing keratinous fibers,particularly human hair.

Thus, an object of the present invention is the provision of a novelcoloring agent useful in a dyeing composition for keratinous fibers,characterized by the fact that said coloring agent comprises at leastone indamine defined above.

When the dyeing composition of the present invention contains as thesole dyeing agent, one or more indamines described above, the colorationimparted to the keratinous fibers by its use varies from green to blond.

However, the dye composition of this invention can also include, inaddition to the indamines defined above other dyes ordinarily used fordyeing hair. Representative of such other dyes are, for example, anilineor anthroquinone dyes. Indoanilines, indophenols or indamines other thanthose defined above.

The novel dye compositions of this invention comprise an aqueoussolution of the said indamine, which dye compositions can be prepared bydissolving in an aqueous medium one or more of said indamines and, ifdesired, one or more conventionally employed dyes useful in thecoloration of keratin fibers. Additionally, however, the dye compositionof this invention can also contain thickeners and thus be in the form ofa cream or gel.

Furthermore, the dye composition of the present invention can alsocontain various conventional ingredients usually employed in cosmeticpreparations, for example, wetting agents, dispersing agents, swellingagents, penetration agents, softeners or perfumes. It has also beenfound that the dye composition of this invention can be in the form of asprayable aerosol, packaged in a conventional aerosol bomb or can.

The pH of the dyeing compositions of this invention can vary withinbroad limits and will range generally between about 5-11, and preferablybetween 7-11. The amount of indamine present in the aqueous solutioncomprising the dye composition of this invention can vary, for instance,depending on, for instance the particular indamines present, the colordesired as well as the color 3 of the hair to be dyed. Thus an amount ofthe indamine effective to produce the desired coloration is employed.Generally this amount ranges between about 0.02 to 0.25 weight percentof the total aqueous solution.

Dyeing of keratinous fibers, in particular human hair, with the dyeingcomposition of this invention is performed in accordance withconventional dyeing techniques, for instance, by applying the saidcomposition to the fibers to be dyed, permitting the composition toremain in contact with said fibers for a period of about 5-30 minutesand thereafter, rinsing and, if desired, washing, and drying the fibers.

The novel indamines of this invention can also be employed to provide anovel hair setting lotion comprising an admixture of at least one ofsaid indamines and a dilute alcohol solution of at least one cosmeticresin.

Cosmetic resins usefully employed to produce said hair setting lotionsinclude, for instance, polyvinylpyrrolidone having a molecular weightranging from about 10,000 to 700,000, copolymers of crotonic acid-vinylacetate, copolymers of vinylpyrrolidone-vinyl acetate wherein the ratioof PVP to PVA can range between, for instance, 50-70150-30, copolymersof maleic anhydride-butylvinyl ether and the like. These resins aregenerally used in the proportion of l to 3% by weight of the totalcomposition. Further the indamine content of said hair setting lotionusually ranges between about 0.02 to 0.25 weight percent of the totalcomposition.

The alcohols suitable for making said hair-setting lotions are loweralkanols, preferably, ethanol and isopropanol. These alcohols are usedin a proportion of 20 to 50% by weight of the total composition.

The hair-setting lotion according to the invention is employed in aconventional manner by applying the same to previously washed and rinsedwet hair, followed by rolling the treated hair on curlers and thereafterdrying it The following examples are given to illustrate the presentinvention. The temperatures indicated in the examples are expressed indegrees Celsius and unless otherwise specifically stated, all parts andpercentages are by weight.

EXAMPLE 1 N-[(hydroxy-6 oxa-l aza-4tetrahydro-l,2,3,4)naphthy1-7]methyl-2 benzoquinonediimine is preparedaccording to the following reaction:

=NEH2O o 0.06 mole (9.06 g.) of hydroxy-6 phenomorpholine is dissolvedin 600 cm. of water. To this solution there are added 18-0 cm. ofammonia at 22 B, 750 cm. of volume hydrogen peroxide and a solution of0.12 mole (14.64 g.) of paratoluylenediamine' in 600 cm. of water. Theresulting reaction mixture is allowed to stand for four hours at ambienttemperature and thereafter 6.5 g. of crystallized indamine, identifiedabove, in monohydrate form is, isolated by filtering off the reactionmass. After recrystallization of the indamine crystals in adimethylformamide-water mixture, the resulting product exhibited amelting point of 258.

Analysis.--Calculated for C I-I N O -H O (percent): C, 62.71; H, 5.92;N, 14.63. Found (percent): C, 61.81, 62.05; H,,5.9 8, 6.02; N, 14.59,14.79.

EXAMPLE 2 N-[(hydroxy-6 oxa-I aza-4 tetrahydro-1,2,3,4)naphthyl-7]methoxy-3 benzoquinonediimine is prepared in accordance withthe following reaction:

H NH:

OH OCH:

0.025 mole (5.27 g.) of methoxyparaphenylenediamine dichlorhydrate isdissolved in 200 cm. of water. The-pH of this solution is then adjustedto a pH of 8 by adding ammonia thereto. To this alkaline solution thereis immediately added 0.02 mole (3.02 g.) of hydroxy--phenomorpholine,previously dissolved in 200 cm. of water. To this resulting mixturethere are added cm. of ammonia at 22 B. and 260 cm. of 20volume hydrogenperoxide. This resulting reaction mixture is then permitted to stand fortwo hours at ambient temperature. The reaction mixture is then filteredoff and there is obtained 3.8 g. of crystallized indamine in monohydrateform which, after washing with water and recrystallization in adimethylformamide-water mixture, exhibits a melting point of 216.

Analysis.Calculated for C H N O -H O (percent): C, 59.40; H, 5.61; N,13.86. Found (percent): C, 58.88, 59.07; H, 5.54, 5.52; N, 13.80, 13.63.

EXAMPLE 3 N-[ (hydroxy-6 oxa l aza-4 tetrahydro1,2,3,4)naphthyl-7]methyl-2 methoxy-S benzoquinone diimine is prepared in accordance withthe following reaction:

0.03 mole (4.53 g.) of hydroxy-6 phenomorpholine is dissolved in 300 cm.of water. To this solution there are added 90 cm. ammonia at 22 B., 350cm. of 20-volume hydrogen peroxide and 0.0375 mole (5.7 g.) of methyl-2methoxy-S paraphenylenediamine in a solution which is a mixture of 50cm. of water and 300 cm. of acetone. The resulting reaction mixture isallowed to stand at ambient temperature for three hours. Then 8.1 g. ofcrystallized indamine in monohydrate form are isolated from the reactionmixture by filtering off the same. After recrystallization in adimethylformamide-water mixture, the product exhibited a melting pointof 226.

Molecular weight found by potentiometric dosing in acetic acid byperchloric acid: 323.

Molecular weight calculated for C gH N o -H O: 317.

Analysis.Calculated for C H N O -H O- (percent): N, 13.24. Found(percent): N, 13.38, 13.30.

EXAMPLE 4 I I N OH H. on.

N 1 on on.

. OCH;

0.02 mole (3.02 g.) of hydroxy-6 phenomorpholine is dissolved in 200c1113 of water. To this solution there are added 0.025 mole (4.1 g.) ofdimethyl-2,6 methoxy-S- paraphenylenediarnine in solution in 200 cm. ofwater, 60 cm. of ammonia at 22 B. and 250 cm. of 20-volume hydrogenperoxide. The resulting reaction mixture is allowed to stand for twohours at ambient temperature and thereafter 3 g. .of crystallizedindamine in monohydrate form are isolated therefrom by filtering off thereaction mixture. After recrystallization in a dimethylformamidewatermixture, the product exhibited a melting point of 186".

Molecular weight calculated for C H N O -H O: 331.

Molecular weight foundby potentiometric dosing in acetic acid byperchloric acid: 333.

Analysis-#Calculated for. C17H19N3O3 -H O (percent): N, 12.68. Found(percent): N, 12.63, 12.82.

EXAMPLE 5 N- (hydroxy-6 oxa-l aza-4 tetrahydro-l,2,3,4 naphthyl- 7JduroquinOhe diimine is prepared in accordance with the followingreaction:

H z III p -oH 3.0- on.

I I O/ 11.0 on.

I IHg n 1 N (W OH CH3 (EH3 0.005 mole (0.75 g.) of hydroxy-Gphenomorpholine is dissolved in 50 cm. of water. To this solution thereare added cm of ammonia at 22 B, 0.01 mole (1.64 g.) of diamino-1,4durene dissolved in a mixture of 30 cm. of water and 40 crn. of:acetone, and finally 75 cm. of -volume hydrogen,peroxide.,This resultingreaction mixture is allowed. to stand at ambientiemperature for fivehours. 0.5 g. of crystallized indamine identified above in monohydrateform, is isolated .by filtering off the reaction mixture. Afterrecrystallization in a dimethylformamide-water mixture, the saidindamine exhibited a melting point of 290.

Molecular weight calculated for C H N O -H O: 329'.

Molecular weight found by potentiometric dosing in acetic acid byperchloric acid: 334.

Analysis.-Calculated for C H N O 'H O (percent) N, 13.07. Found(percent): N, 12.71, 12.80.

EXAMPLE 6 A dyeing composition, in accordance with this invention, isprepared as follows:

The indamine of Example 2 0.1 Lauric alcohol oxyethylenated with 10.5moles of ethylene oxide 5 Water sufficient for 100- g.

This dyeing composition solution is applied to gray hair and left incontact therewith for 30 minutes. The hair is then rinsed and shampooed.A green gray shade is obtained.

. EXAMPLE 7 A hair setting lotion, in accordance with the presentinvention, is prepared as follows:

1 G. Indarnine of Example 2 0.1 Crotonic acid-vinyl acetate copolymer(10%:90%,

mol. wt. 45,000) Ethanol96 titer suflicient for 50. Water sufiicient for100 g.

This hair setting lotion is applied to 100% white hair and impartsthereto a dull green hue.

EXAMPLE 8 A hair setting lotion is prepared as follows:

The indamine of Example 5 0.1

Crotonic acid-vinyl acetate copolymer (l0%:90%,'

mol. wt. 45,000)

Isopropanol-96 titer suflicient for 50.

Water sufficient for 100 g.

This hair setting lotion is applied to 100%, white hair and impartsthereto a golden blond color.

EXAMPLE 9 A hair dye composition is prepared as follows:

The indamine of Example 4 0.2

Butylglycol 5 Lauric alcohol oxyethylenated with 10.5 moles of ethyleneoxide 5 Water sufficient for 100 g.

This hair dye composition is applied to 100% white hair and is permittedto remain in contact therewith for 30 minutes. Thereafter the hair isrinsed and shampooed and a lime coloring is imparted thereto.

EXAMPLE 10 A hair dye composition is prepared as follows:

The indamine of Example 4 0.1 N[(amino 4'methy1- 3')phenyl1amino-3dimethyl- 2,6 benzoquinoneimine 0.1

Ammonia suflicient for pH 10.5. Water sufiicient for 100 g.

The hair dye composition is applied to white hair and permitted toremain in contact therewith for a period of about 30 minutes. The hairis then rinsed and shampooed and a clear chestnut coloring with slightviolet glints is imparted thereto.

EXAMPLE 11 A hair setting lotion is prepared as follows:

G. The indamine of Example 3 0.2

Crotonic acid-vinyl acetate copolymer (10%:90%,

mol. wt. 50,000) 2 Ethanol96 titer, sufiicient for Sl).

Water sufficient for 100 g.

This hair setting lotion is applied to bleached hair and imparts theretoa blond color with Cyprian green glints.

What is claimed is:

1. A process for dyeing human hair which comprises applying to said hairin an amount effective to dye the same an aqueous solution containing0.02-0.25 percent by weight of a dye having the formula wherein R R Rand R each independently represent a member selected from the groupconsisting of hydrogen, halogen, lower alkyl having 1-4 carbon atoms andlower alkoxy having 1-4 carbon atoms, said compound being present in anamount ranging between 0.02 to 0.25 percent by weight of the totalcomposition.

3. The composition of claim 2 wherein the pH of said composition rangesbetween 5-11.

4. The composition of claim 3 wherein the pH ranges between 7-11.

5. The composition of claim 2 wherein the aqueous solution furthercontains a lower alkanol and a film forming resin in amounts of about1-3 weight percent based on the weight of said composition.

6. The composition of claim 5 wherein the lower alkanol is selected fromthe group consisting of ethanol and isopropanol.

7. The composition of claim 5 wherein the lower alkanol is present inamounts ranging from about 20-50 percent by weight of said composition.

References Cited UNITED STATES PATENTS 2,453,661 11/1'948 Glass et al9656.1

GEORGE F. LESMES, Primary Examiner P. C. IVES, Assistant Examiner U.S.Cl. X.R.

